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Thermodynamics of Li-Si and Li-Si-H phase diagrams applied to hydrogen absorption and Li-ion batteries

机译：Li-Si和Li-Si-H相图的热力学应用于氢吸收和锂离子电池

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A consistent thermodynamic description of the Li-Si system and its extension to the Li-Si-H system is developed based on comprehensive Calphad-type assessment of all pertinent thermodynamic and phase equilibrium data. Key experiments were performed by measuring the equilibrium pressure for the hydrogenation of the lithium silicides at 773 K, 748 K and 723 K. The Gibbs energy functions of the Li-Si compounds developed in this work are validated by direct comparison of the predicted hydrogen pressure with experimental data. The interrelation of the hydrogen absorption pressure with the calculated Li-Si-H ternary phase diagram is also elucidated. The calculated Li-Si phase diagram, both on chemical potential and composition scale, is well supported by the entity of experimental data. In addition to the stable intermetallics Li17Si4, Li16.42Si4 (Li4.11Si), Li13Si4, Li7Si3, Li12Si7, LiSi also metastable Li15Si4 and an approximate for amorphous Si(Li) is included in the thermodynamic modeling. Qualitative prediction of open-circuit voltage curves during metastable lithiation/delithiation of Si as advanced anode material for Li-ion batteries at room temperature is made. (C) 2017 Elsevier Ltd. All rights reserved.
机译：基于对所有相关热力学和相平衡数据的全面的Calphad型评估，开发了Li-Si系统的一致热力学描述及其对Li-Si-H系统的延伸。通过测量773k，748k和723k的硅化物氢化的平衡压力来进行关键实验。通过直接比较预测的氢气压力，通过直接比较来验证在该工作中产生的Li-Si化合物的Gibbs能量功能用实验数据。还阐明了氢吸收压力的相互关联也阐明了氢吸收压力。计算出的LI-SI相图，既通过实验数据的实体很好地支持了化学势和组成量表。除了稳定的金属间化合物Li17Si4，Li16.42Si4（Li4.11si），Li13Si4，Li7Si3，Li12Si7，Li12Si7，Li12Si7还含有亚稳Li15SI4和无定形Si（Li）的近似包括在热力学建模中。制备了在室温下作为锂离子电池的稳定锂电层/锂电片的稳态锂化/脱垂期间的开路电压曲线的定性预测。 （c）2017 Elsevier Ltd.保留所有权利。

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